Azo dye.



UNITED STATES PATENT OFFICE.

FRIEDRICH RUNKEL AND MARTIN HERZBEBG, OF ELBERFELD, GERMANY, ASSIGNORS TO FARBENFABRIKEN VORM. FRIEDR. BAYER & (30., OF ELBERFELD, GERMANY,

A CORPORATION OF GERMANY.

AZO DYE.

No Drawing.

invented new and useful Improvements in Azo Dyes, of which the following is a specivfication.

Our applications Serial No. 490,226 and Serial. No. 490,227 relate to the manufacture and production of new azo dyes which can be obtained by combining the diazo compounds of one molecule of aminophenylothers or their homologues and one mole cule of any other diazo compound in any course of succession with one molecule of a periamino-naphtholsulfonic acid. The new dyestutts thus obtained dye wool from blue to green to black shades remarkable for their fastness to washing and to milling alongside with cotton and wool. We have now found that dyestuffs of the same Valuable properties can be obtained on using in the above mentioned process halogen substituted derivatives. of aminophen'ylethers or their homologues e. g. ortho-amino-parachlorophenylether, ortho-aInino-para-chlorophenyl-meta-tolylether, ortho-amino-para- -chlorophenyl-para-tolylether, ortho-aminoortho -chlorophenylether,ortho-amino-para chlorophenylether, ortho amino-para-chlorophenyl ortho chlorophenylether, orthoamino-para-chlorophenyl -para chlorophenylether, para-aminocrtho -chlorophenylether, para amino para chlorophenylether, para-amino-ortho-chlorophenyl-parafchlorophenylether, which can 6. g. be ob-- tained by the process described in Bem'ckte de'r De-utschen Ohemz'scken Gesellschaft 29 p. 1446. V

The new dyestulis are after being dried and pulverized in the shape of their sodium salts dark powders soluble in water. Upon reduction with stannous chlorid and hydrochloric acid they are decomposed, a halogen substituted aminophenylether an amino compound and a diamino 1.8-aminonaphthol sulfbnic acid are obtained. The new coloring matters dye wool from blue to green to black shades remarkable for their fastness to washing and to milling.

In order to illustrate the new process more fully the'following examples are given, the parts being by we1ght:

Specification 'of Letters Patent.

to be stirred for about 10 hours.

Patented Feb. 22, 1910.

Application filed July 22, 1909. Serial No. 508,985.

Example 1: 22 parts of para-chloro-orthoaminophenylether are dissolved in a hot mixture of 90 parts of concentrated hydrochloric acid and 350 parts of water. The ether is then quickly diazotized in the usual .way. After cooling the hydrochloric acid is neutralized with soda so'that the mixture is only weakly acid and the diazo compound is introduced into a. cold aqueous weaklyacid solution of 31.9 parts of 1.8.4.6-aminonaphthol distilfonic acid. It is stirred for some hours "at the ordinary temperature. After the addition of soda 13.8 parts of diazotized meta-nitranilin are then added. The dyestufi which precipitates is filtered off, washed with alkaline water and dried. It dyes wool from acid baths black shades.

Example 2: 16.2 parts of 2.5-dichloroani lin are dissolved in 160 parts of hot water and 160 parts of hot crude hydrochloric acid, ice is added and the dichloroanilin is diazotized with 7.1 parts of sodium nitrate.

50 per cent. of the excess of hydrochloric acid is'then neutralized with sodium carbonate and 31.9 parts of freshly precipitated 1.8.3.6-a1ninonaphthol disulfonic acid are added to the mass of the reaction which has After it has been rendered alkaline with sodium carbonatethe diazo compound of 22 parts of para-amino=para -chlorophenyleth er is added. After some time the precipitated dye is filtered off, redissolved from hot water, filtered ofi', pressed anddried. It is after being dried and pulverized in the shape of its sodium salt a dark powder soluble in water with a blue color. and soluble 'in concentrated sulfuric acid with a dark blue color. Upon reduction with stannous chlorid and-hydrochloric acid the new dye is decomposed. 2.5-dichloroanilin, paraamino para chloro phenylether and 1.2.7

triamino-B-naphthol-3.6-disultonic acid are Corrections in letters Patent No. 950,404.

l. The herein described new diazo dyestntts obtainable from 1 molecule of a diazotized halogen substituted aminoarylether, 1 molecule of another diazo compound and 1 molecule of n- L8-aminonaphthol sulfonic acid, which are after being dried and pulverized in the shape of their sodium salts dark powders soluble in water; yielding upon reduction with 'stannous chlori'd and.

hydrochloric acid a halogen substituted It; is hereby certified that in Letters Patent No. 950,404, granted l ebruary sult'onic acid, which dye is after being dried and pulverized in the shapeof its sodium salt a dark powder soluble in water with a blue -olor and soluble in comrentrated sulfuric acid with a dark blue color; yielding; u )on reduction with stannous ehlorid and by r0- chloric acid para-amino-pa ra-chloro-pheny1- ether, diehloroanilin and 1.2.7-triamino8- nu11hthol-3.t3-diHultonic acid; and dyeing wool blue-black shades remarkable for their t'a tness to washing and to milling, substantially as described.

in lflHilll'lOlly whereof we have hereunto set our hands in the presence of two subscribing witnesses.

ERIE DRICII BUNK I) L. Ir. SQ] UAR-TIN HER'ZBERG. in. \-\"it.nes; :es:

()r'ro Kiln Io, \V I LLY K L'm upon the'application of Friedrich llunkeland Martin H'erzherg. of lllberteld. Ger many, for. an in'iproveinent-in fAzo llyea," errors appear in the printed speritieation requiring correction 'as' follows: Page 1. line T6. the word nit-rate should read min-57b, and same page, liries' 7 and 90 the. word is"-sh0uld read me; and that. the eaid LettersIPa tent nhould he read with these. correction;therein that the same n'nri" eonforn'l to the record ot'the ease in the latent. ()ttiee. v

"Signed and sealed this 26th day of April. A. -l).., 191d.

e. e. BILLJNGS,

Corrections in letters Patent No. 950,404.

l. The herein described new diazo dyestntts obtainable from 1 molecule of a diazotized halogen substituted aminoarylether, 1 molecule of another diazo compound and 1 molecule of n- L8-aminonaphthol sulfonic acid, which are after being dried and pulverized in the shape of their sodium salts dark powders soluble in water; yielding upon reduction with 'stannous chlori'd and.

hydrochloric acid a halogen substituted It; is hereby certified that in Letters Patent No. 950,404, granted l ebruary sult'onic acid, which dye is after being dried and pulverized in the shapeof its sodium salt a dark powder soluble in water with a blue -olor and soluble in comrentrated sulfuric acid with a dark blue color; yielding; u )on reduction with stannous ehlorid and by r0- chloric acid para-amino-pa ra-chloro-pheny1- ether, diehloroanilin and 1.2.7-triamino8- nu11hthol-3.t3-diHultonic acid; and dyeing wool blue-black shades remarkable for their t'a tness to washing and to milling, substantially as described.

in lflHilll'lOlly whereof we have hereunto set our hands in the presence of two subscribing witnesses.

ERIE DRICII BUNK I) L. Ir. SQ] UAR-TIN HER'ZBERG. in. \-\"it.nes; :es:

()r'ro Kiln Io, \V I LLY K L'm upon the'application of Friedrich llunkeland Martin H'erzherg. of lllberteld. Ger many, for. an in'iproveinent-in fAzo llyea," errors appear in the printed speritieation requiring correction 'as' follows: Page 1. line T6. the word nit-rate should read min-57b, and same page, liries' 7 and 90 the. word is"-sh0uld read me; and that. the eaid LettersIPa tent nhould he read with these. correction;therein that the same n'nri" eonforn'l to the record ot'the ease in the latent. ()ttiee. v

"Signed and sealed this 26th day of April. A. -l).., 191d.

e. e. BILLJNGS, 

